Identification and Synthesis of the Male-produced Sex Pheromone of the Stink Bug, Pellaea stictica

Abstract

Stink bugs are major pests of a wide variety of agricultural crops worldwide. The species Pellaea stictica is a Neotropical stink bug found in several South American countries. Chromatographic analyses of volatiles released by adults of this species showed that males produce a sex-specific compound, and bioassays with a Y-tube olfactometer showed that the compound was attractive only to females, confirming that it is a sex pheromone. Gas chromatography coupled to mass spectrometry and Fourier transform infrared analyses of the natural compound and several derivatives suggested that the structure was an alcohol with a saturated carbon chain and several methyl branches. After synthesis of two proposed structures, the pheromone of P. stictica was identified as a novel compound, 2,4,8,13-tetramethyltetradecan-1-ol. Laboratory bioassays showed that the synthesized mixture of stereoisomers of 2,4,8,13-tetramethyltetradecan-1-ol was as attractive to P. stictica females as the natural pheromone.

Asymmetric Synthesis of Contact Sex Pheromone of Tetropium fuscum and Its Enantiomer

“…Its specific rotation {[α] D 22 = −9.0 ( c 1.37, CHCl 3 )} was identical to the literature [ 21 ] value {[α] D 23 = −8.4 ( c 1.00, CHCl 3 )}, which also supported the ( S )-configuration of the new stereocenter. The final Appel reaction converted the chiral methyl alcohol ( S )- 6 to ( S )-1-bromo-2-methyldodecane (( S )- 7 ) in a 99% yield [ 22 , 23 ]. Similarly, ( R )-1-bromo-2-methyldodecane (( R )- 7 ) was prepared via acylation, diastereoselective methylation, reduction, and bromination from dodecanoic acid ( 2 ) and ( R )-4-benzyloxazolidin-2-one (( R )- 3 ).…”

Recent advances in the synthesis of insect pheromones: an overview from 2013 to 2022

“…7 shows the methyl-branched pheromones of Tenebrio molitor (Col., Tenebrionidae): (R)-156, [124][125][126][127][128] Oryctes rhinoceros (Col., Dynastidae): 157, [128][129][130][131] Kheper nigroaeneus (Col., Scarabaeidae): (R)-158, 126,128,132 Oryctes rhinoceros (Col., Dynastidae): 159, 133 Euproctis pseudoconspersa (Lep., Erebidae): 160, 134,135 Miltochrista calamina (Lep., Erebidae): (5R,7R)-161 136,137 palm weevils (Col., Curculionidae): (4S,5S)-162 and (4S,5S)-163, 138 Rhynchophorus ferrugineus (Col., Dryophthoridae): 164, 165, 133,139 Scolytus multistriatus (Col., Curculionidae): 166, 140 Sitophilus granarius (Col., Dryophthoridae): 167, 141 Diabrotica longicornis (Col., Chrysomelidae): (2S,8R)-168, 142,143 Bicyclus spp. (Lep., Nymphalidae): 169, 144 Cryptothelea variegata (Lep., Psychida): (3R,13R,3 ′ S)-170, 145,146 Eurytoma maslovskii (Hym., Eurytomidae): (2S,10R)-171, (2S,8S)-and (2S,8R)-172, 147 Pellaea stictica (Hem., Pentatomidae): 173, 148,149 Edessa meditabunda (Hem., Pentatomidae): 174, 150 Trichogramma turkestanica (Hym., Trichogrammatidae): 175, 151 Margarodes prieskaensis (Hem., Margarodidae): 176, 177. 152 The asymmetric synthesis of 10,14-dimethyl-1-pentadecyl isobutyrate (160), the sex pheromone of the tea tussock moth Euproctis pseudoconspersa, was performed by Zhang et al (Scheme 12).…”